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Патент USA US3091545

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Latent
United
1
3,091,535
“ice
3,091,535
Patented May 28, 1963
2
organic colloid of high molecular weight as a binding
agent, (3) a photographic silver halide emulsion layer on
the translucent layer and on the other surface of the
PHOTOGRAPHIC FILM ELEMENT WITH
base (4) an antihalation layer comprising a binding
ANTIHALATION LAYER
Clifford E. Milner, Jr., Rochester, N.Y., assignor to E. I. 5 agent, colloidal antihalation material, e.g., a dye or pig
ment, and ?nely divided particles of a white pigment is
du Pont de Nemours and Company, Wilmington, Del.,
described for the translucent layer.
a corporation of Delaware
In general, the white pigment is present in an amount
No Drawing. Filed Dec. 31, 1959, Ser. No‘. 863,085
from 1.5 to 3.0 parts by weight per part of binding agent.
6 Claims. (Cl. 96-—84)
The antihalation dye or pigment in general will be col
The present invention relates to photographic elements 10 loidal (in the range of 1 to 100 millimicrons) in their
and more particularly it relates to photographic ?lms.
Still more particularly it relates to photographic trans
largest diameter. The amount of antihalation material
present is that used in conventional antihalation layers
and in general comprises ‘0.05 to 0.10 part per part of
lucent print ?lms having improved antihalation and
resolution characteristics.
15 binding agent.
Photographic emulsions on translucent to opaque ?lm
supports have a wide variety of applications in the ?elds
of cartography, transilluminated display and mural Work,
drafting and chart work, and technical and sales manuals.
It has been proposed to make such ?lms by coating a 20
photographic emulsion on one side of a transparent ?lm
support and coating on the opposite side of the support
a translucent layer containing an opaque substance and
which may or may not contain an antihalation dye. It
The support may be any conventional transparent
hydrophobic ?lm such as cellulose esters, e.g., cellulose
acetate, cellulose nitrate, cellulose butyrate, cellulose
mixed esters; vinyl polymers, e.g., polyvinyl acetate, poly
vinyl chloride, polyvinylidene chloride, polystyrenes and
copolymers thereof; polyamides, e.g., polypentamethylene
sebacamide, polyhexamethylene sebacamide, polypenta
methylene suberamide, polydecamethylene adipamide and
superpolyesters, e.g., a highly polymeric linear polyester
has also been proposed to prepare such ?lms by coating 25 of a dicarboxylic acid with a dihydric alcohol. A pre
on one side of a transparent ?lm support, in order, a slow
fered type of support comprises a polyester ?lm as dis
speed emulsion containing an opalescent substance such
closed in Whin?eld et al. US. 2,465,319 bearing a thin
as starch or rubber latex and a fast speed silver halide
layer of an adherent ?lm-forming essentially hydropho
emulsion. On the opposite side there may be coated a
bic copolymer made and coated in the manner taught by
plain gelatin layer ‘or a layer containing an antihalation 30 Alles et al., U.S. Patent 2,627,088, and Alles, US. Patent
dye. Both of these proposals leave much to be desired
2,779,684, and patents referred to in the speci?cations of
in the way of good resolution and antihalation qualities.
these patents. A ?lm made according to Example IV of
Further, it has been proposed to coat an antihalation
Alles US. Patent 2,779,684 which may or may not be
layer between the emulsion layer and the support. This
coated with a thin gelatin substratum is coated on one
type of structure has some very serious disadvantages.
surface with an aqueous gelatin dispersion comprising
When such elements are exposed and processed, the prints
from about 30 to 50% of gelatin and from about 50 to
resulting therefrom are often stained in an unsightly man
70% of titanium dioxide based on total dry weight to give
ner which results in failure to obtain the desired white
a layer having a dry coating weight of about 10mg./dm.2
background for re?ection viewing. This is caused by
of gelatin. Over this layer, any suitable light-sensitive
inadequate bleaching or color destruction during process 4.0 layer may be coated. Gelatino-silver halide emulsions
ing due to the presence of the emulsion layer which re
are preferred, however. For example, the variable gam
tards diffusion of treatment solutions into and out of the
ma gelatino-silver halide emulsions dislcosed in Potter
non-halation layer. In addition, placing antihalation
et al. US. Patent 2,280,300‘ have been found to be partic
material in a layer contiguous with the silver halide layer
ularly useful. The type ‘of light-sensitive layer will,
often aifects the sensitometric characteristics by produc 45 however, depend on the manner in which the novel ?lm
ing fog. Another proposal has been to coat a white
elements are to be used. On the opposite side of the
water-resistant support with a silver halide emulsion on
?lm there is coated an aqueous gelatin dispersion contain
one side and tinted layer on the opposite side. An alter
ing from about 50 to 70% of titanium dioxide and from
about .25 to 10% of colloidal manganese dioxide. The
pigment coating on top of which there is coated a silver 50 layer is coated and dried in a conventional manner to give
halide emulsion. These latter elements are also de?cient
a dry weight about 70 mg./dm.z of gelatin. To increase
in providing satisfactory resoution and antihalation
the utility of the novel ?lm, delustering or matting agents,
i.e., silica, starch, etc., may be added to the molten
qualities.
An object of this invention is to provide improved
gelatino-silver halide emulsion as a ?nal addition before
translucent photographic print ?lms. Another object is to 55 coating to form a retouchable yor drawing surface on the
provide such ?lms which have improved antihalation
emulsion side of the ?lm. For example, the highly porous
and resolution characteristics. Yet another object is to
siliceous compounds disclosed in Webster US. Patent
provide such ?lms which are relatively simple in construc
2,626,867 are suitable for this purpose.
tion and embody commercially available and economical
Titanium dioxides of various crystalline forms may
antihalation materials and pigments. A further object 60 be used as the white pigment, however, the rutile crys
is to provide such ?lms which do not produce objection~
talline form is preferred because of its greater “hiding
able stain when the exposed ?lms are developed ‘and ?xed.
power” (greater opacity for a given weight). Other
A still further object is to provide such ?lms which can
white pigments such as barium sulfate can also be used.
Likewise, while colloidal manganese dioxide is preferred
be made by the use of conventional mixing and coating
apparatus. Still further ‘objects will be apparent from 65 as the bleachable non-halation coloring component, other
native method is to coat a tinted support with a white
the following description of the invention.
The photographic elements of the present invention
have (1) a transparent hydrophobic copolymer ?lm base,
(2) a translucent layer on one side of the base compris
ing dispersed ?nely divided particles of an inert inorganic
white pigment having an average particle size in the range
0.1 to 2.0 microns in a water-permeable macromolecular
bleachable non-halation dyes or pigments, i.e., Aur-amine
(C. 1.655), Acid Blue Black (C. 1.246) and Nigrosine
(C. 1.864) may be used. Other ingredients for various
purposes may be added to any one or all of the layers.
For example, ‘so-called “optical brightener,” i.e., com
pounds which ?uoresce under the in?uence of visible
radiation to increase the brightness of the layers, may be
3,091,535
3
4
added to the molten gelatino-silver halide emulsion, to the
aqueous gelatin-titanium dioxide dispersion and/or to
the aqueous gelatin-titanium dioxide-manganese dioxide
dispersion as a ?nal addition before coating.
The invention will now be illustrated in and by the
following examples, but is not intended to be limited
?cient exposure was given to cause inversion of the image
by solaiization under the lightest part of the wedge. At
this level of exposure the image of the slit is bordered
on either side, at a distance which depends on the thick
ness of the ?lm support, by two bands due to halation.
The e?iciency of antihalation protection can be measured
as the ratio of the exposures corresponding respectively
to the threshold of halation and the threshold of blacken
thereby.
Example I
A dimensionally stable vinylidine chloride/methyl
acrylate/itaconic acid copolymer-coated polyethylene
10
terephthalate ?lm made as described in Example IV of
~Alles US. Patent 2,779,684 Was coated on one surface
‘with an aqueous dispersion containing 3.5% gelatin and
7.0% of rutile'crystalline titanium dioxide (Du Pont “Ti
ing of the bands.
The resolution was determined by the method outlined
in National Bureau of Standards Circular C248, “A Test
of Lens Resolution for the Photographer.”
‘Opacity was determined as the transmission density to
blue light. The measurements below show the compari
Pure” R-1-00) based on the total weight and to which 15 son of the novel ?lms of the inventions with ‘known
structures.
‘had been added a small amount of an alkyl naphthalene
isulfonate Wetting agent and a small amount of a bis-tri
azinostilbene compound as an optical brightening agent.
Backing
The dispersion was coated at 56 feet per minute to give
Underlayer
Reso-
Opacity lution
a dry gelatin coating weight of 10 -mg./dm.2. Over this 20
layer, there was coated a high speed variable contrast
silver iodo-bromide emulsion containing 3%v iodide and
and dried in a conventional manner.
Stain
1. White+bleach~
White-l-bleach-
1.10
122.
44
Bad.
White _________ __
1.10
107
40
‘None.
______do _________ __
1.10
137
27
White+bleach~~
ab color.
1.10
137
36
Bad.
5. Single weight paper base _________ __
1.30
77
50
Good.
able col
The emulsion was 25
made in the manner described in 'Potter et al. U.S. Patent
hala~
2. White-l-bleach-
able color.
the rest being silver bromide and 73% gelatin based on
‘total weight of dry solids. The emulsion was coated
Anti
tion ‘1
able color.
Do.
‘2,280,300 and contained 0.12 gram/gram of dry gelatin
of highly porous S102 as a matting agent to provide a
retouchable surface. There was also added to the molt
1 The larger the number, the better the antihalation characteristics.
Example I]
en emulsion before coating a small amount of the above 30
optical brightening agent and 140 mg./mole silver halide
of lbenzotriazole as an antifoggant. The dry coating
weight was 133 mg./dm.2 of silver halide expressed as
AgNO3.
On the opposite side of the ?lm there was coated an
Example I was repeated except that in place of the
variable contrast silver iodo-bromide emulsion of that
example‘there was coated argelatino-silver chlorobromide
emulsion. The emulsion contained ‘about 34% silver
35 chloride and the rest silver bromide. The .emulsioncon
trained a delustrant-as a matting agent to ‘provide a ‘re
aqueous dispersion containing 6% gelatin, 12% .rutile
touchable surface as is conventional in the art.
crystalline titanium dioxide, and 0.4% colloidal manga
nese dioxide.
expressed as AgNO3.
give a dry gelatin coating weight of 70 mg./dm.2.
The resulting photographic film element was exposed
by conventional projection enlarging equipment.
The backing was coated to a
dry weight of v80 mg./dm.2 of gelatin (instead of 70
mg./dm;2). The resulting ?lm had similar characteristics
The
exposed ?lm was developed ‘for 11/2 minutes at 20° C. ,
in'a developer having the following composition:
The
dry coating had a weightof 22 mg./dm.2 of silver-halide
This aqueous dispersion was coated to
to the ?lm of Example 1. Because of the warm image
color and response to direct toning, the product was par
ticularly suited to portrait and photomini-ature applica
Grams 45 tion requiring special effects.
p-Methylaminophenol sulfate ________________ __
2.5
Example III
Hydroquinone _____________________________ __ 10.0
Sodium sul?te (anhydrous) __________________ __ 37.5
Sodium carbonate, monohydrated ____________ __ 44.0
‘Potassium bromide _________________________ __
5.0
Water to make 1 ‘liter.
The above developer .was used by diluting with two parts
vofrwater. The ‘?lm was then ?xed in a photographic ?xer
Example I was repeated except that in place of the
emulsion of that example, there was coated a high con
50 trast contact speed bromochloride emulsion containing
30% silver bromide and 70% silver chloride. The dry
coating weight was 22 mg./dm.2 of silver halide expressed
as AgNO3.
The backing was coated to a weight of 40
mg/drn.2 of gelatin. A planar, non-curling ?lm was
obtained whichwas exposed in a conventionalcontact
55
Sodium thiosulfate _________________ __grams— 240.0
printer for 20‘ seconds at 15 feet using a ‘single 50
having the following composition:
Sodium sul?te, anhydrous ____________ __do____
15.0
ampere arc lamp.
'Glacial'acetic acid ____________________ __ml.__
‘Potassium aluminum sulfate __________ __grams__
47.0
15.0
minutes at.20° C. in a developer having the following
‘Water to make 1.0 liter.
The ?lm was developed for 21/2
composition :
Grams
.p-Methylaminophenol sulfate _____ ___ ________ __
1.5
The ?xed ?lm was washed for 30 minutes and dried in
Hydroquinone _________________________ _______
6.0
a conventional manner. The resulting processed ?lm
Sodium sul?te, anhydrous ___. _______________ __ 19.5
element showed good sensitometric characteristics with no
Sodium carbonate, monohydrated ____________ __ 28.0
evidence of residual stain which results when manganese
dioxide or other bleachable coloring matters are placed 65 Potassium bromide _____ __.__________________ __ 0.8
Water to make 1.0 liter.
in a layer between the support and the gelatino-silver
halide emulsion layer. The ?lm also showed good anti
The ?lm was then ?xed for ten minutes in the ?xing
composition set forth in Example I. The ?lm showed ex
halation and resolution characteristics as compared to
conventional paper supports coated with similar emul
cellent sensitometric resolution and non-halation charac
sions. In addition, the resulting print was markedly 70 teristics.
superior to the prior art ?lms described above. In test
Example IV
ing the ?lm elements for halation, they were exposed
behind ‘a neutral wedge with a density range of 0 to 7 over
a length of 12 cm. and a mask with a 1 mm. slit with
Example ‘I was repeated except that-in place of the silver
halide emulsion of that example, there was coated a high
contrast direct positive silver chloride emulsion to a dry
clean cut-edges parallel to theslope of the wedge. Suf 75 weight of 35 rng./dm.2 of silver ‘halide expressed as
3,091,585
6
photographs, commercial displays, murals, education de
AgNO3. The ?lm was exposed through an amber ?lter
to a high intensity mercury vapor lamp. The exposed ?lm
was developed for one minute in the developer described in
Example '1 but diluted 1:1 with water. The ?lm was
?xed for 10 minutes in the ?xing composition described
vices, etc.
For all applications, the planar, non-curling character
istics offer superior advantages over paper based products.
For example, because of the durability of the ?lms of the
instant invention they are especially applicable to making
in Example I. The resulting direct positive image showed
sales manuals and instruction charts, etc.
In addition, because of the superior dimensional stabili
good resolution and non-halation characteristics.
Other emulsions such as cold tone projection and con
ty of the novel ?lms they are especially useful in the ?eld
tact speed emulsions may also be coated on the novel ?lm
10 of aerial mapping and general survey mapping.
structures to advantage.
For transilluminated displays, a striking effect can be
All or a portion of the gelatin for the various layers
may be replaced by other water-permeable colloids. For
example, natural or synthetic, essentially hydirophilic
polymers may be used to form the aqueous dispersions.
Casein, albumin, interpolyamides, agar-agar, polyvinyl
alcohol, polyacrylamides and polyvinylacetals may be
achieved by coloring only the side opposite the silver
halide emulsion layer with appropriate colors. With re
?ection lighting only, the print appears black and white,
15 but with transmission lighting the image appears in color.
In this application, non-penetrating coloring matters are
most suitable.
What is claimed is:
used. In addition, certain other polymers or polymer mix
tures such as polyvinyl-N-vinyllactams, butadiene-acrylo
nitrile copolymers, vinyl acetate-vinyl stearate copolymers,
styrene-butadiene copolymers, alkyd and acrylic resins
20
may be used in combination with gelatin.
Supports other than those mentioned above are poly
ethylene terephthalate/isophthalate of the British Patent
766,290 and Canadian 562,672 and those obtainable
by condensing terephthalic acid or dimethylterephthalate 25
with propylene glycol, diethylene glycol, tetramethylene
glycol or cyclohexane-1,4-dimethanol (hexadydro-p-xy
lene alcohol).
Other bleachable coloring materials may be used in
place of colloidal manganese dioxide although it is pre 30
ferred because of its greater stability under adverse storage
conditionings. For example, the coloring materials dis
closed in Baldsiefen, US. Patent 2,203,7 67 may be used.
Other white pigments may be used in place of the
rutile crystalline titanium dioxide mentioned above, e.g., 35
barium sulfate, calcium sulfate and zinc oxide.
The unexpected and advantageous result is that the
1. A translucent photographic print ?lm comprising
(1) transparent hydrophobic copolymer ?lm base,
(2) a translucent layer on one surface of the base
comprising dispersed ?nely divided particles of an
inert inorganic white pigment having an average par
ticle size in the range 0.1 to 2.0 microns in a water
permeable macromolecular organic colloid of high
molecular weight as a binding agent, there being 30
to 50%, by weight, of colloid and 50 to 70%, by
weight, of said pigment,
(3) a photographic silver halide emulsion layer on
the translucent layer, and on the other surface of the
base
(4) an antihalation layer comprising a water-permeable
colloid binding agent, bleachable colloidal antihala
tion material and ?nely divided particles of the white
pigment and having the particle size de?ined in layer
(2), said antihalation layer having a coating weight
of 40 to 80 mg. per sq. dm. of colloid, there being
present about 50 to 70% of the white pigment and
about 0.25 to 10% of the antihalation material,
based on the colloid.
2. An element according to claim 1 wherein said pig
ment is titanium dioxide.
3. An element according to claim 1 wherein said pig
ment is titanium dioxide, the binding agent is gelatin
Sensito
metric
Compati— 45 and layer (2) has a coating weight of about 10 mg. per
bility
sq. dm. of gelatin.
4. A photographic print ?lm as set forth in claim 1
antihalation and resolution characteristics of the novel
structure are surprisingly good. The following is a com
parison of the characteristics of prior art structures with 40
those of the novel structures of the instant case.
Backing
Under layer
White-i-bleachable
White+bleach-
color.
able color.
Do _____________ _. Wh?ite pigment
0
White only.
____ ..
AntiHalation
Stain
Good.
y.
White only ______ __
Do ............. .. White + bleach-
wherein said colloid binding agent in each of layers (2)
and (3) is gelatin.
Good.... Bad... Poor.
_--do.--. None
P0or.... __.do_-
50
Do.
.--do_--. Bad-.- Poor.
able color.
5. A photographic print ?lm as set forth in claim 1
wherein said antihalation material is manganese dioxide.
6. A photographic print ?lm as set forth in claim 1
wherein said emulsion layer is a gelatino silver iodo
bromide emulsion layer.
It will be seen from the above data that the white 55
underlayer in conjunction with the white bleachable back
ing (2) gives surprisingly good halation protection with
out the problems of possible incompatibility of the bleach
able coloring material with the photographic emulsion or
residual stain from inadequate bleaching due to the 60
presence of the emulsion layer barrier.
Because of the ease of coloring both back and front and
because of the translucency characteristics, these prod
ucts are particularly well-suited for trans-illuminated
References Cited in the ?le of this patent
UNITED STATES PATENTS
1,597,727
De ’Sperati ___________ __ Aug. 31, 1926
1,631,421
2,095,018
2,313,570
2,698,235
2,773,769
Lohofer _______________ __ June 7,
Wilmanns et a1. ________ _- Oct. 5,
Nadeau et al ___________ __ Mar. 9,
Swindells ____________ __ Dec. 28,
Goldschein ___________ __ Dec. 11,
1927
1937
1943
1954
1956
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